Triazine derivatives



W Patented s r. ;7, 1943 mu e: v

r butyl, H

: DFSTATES PATENT o 'GaetanoYF. b Alelionnd JamesW.Underwood, l i Pittsfield,Massa assignors to Generall Electric Colnminy, a corporation of New York In;the above formulan represents an integer and is at least flland not more'than 2,R fepre l sentsa member or the class consisting ofhydro- "gen "and'monovalent hydrocarbonand substituted hydrocarbon radicals, more particularly halohydrocarbon radicals, and R represents amemv Illustrative examples of monoyalent aliphatic and aromatic, 'hydroearbpn radicals thatjB' in; the abovefformula "mayfrepresjent are radicals such as abovelmentioned with reference to Illustrative examples of monovalent, nuclearly substituted," specifically nuclearly halogenated, aromatic hydrocarbon radicals that Rf also may represent areza -c hlorc phenyl, dichlorophenyl,

10 t t n 'ronaphthyl, ,dijchloronaphthyl'; chloroxenyl, di

chloroxenyl, bromoxenyland thelike;

ber of the class consisting of monovalent aliclearly halogenated, aromatic hydrocarbon radi- 1w ra veL. mn le f e i a het i in th above formula may represent are aliphatic (e, g.,

methyl, ethyl, propyl, isopropyl, butyl, secondary t c b iph a. cy lo e t l; rcl n e y ntolyl, xylyl; ethylphenyl, propylp'henyl, isopropylph l: ally p e y L zrbuten p t r i butylphenyLetcJ; aryl-substituted aliphaticmge.

.lg.,' ben zyl, cinnamy1, phenylethyl, phenylpropyl,

etc.) and their homologues; as well i as those groups with one or more of their hydrogen atoms substituted by, forexampla;a halogen, morepar, ticularly chlorine, bromine; fluorine or iodine, v specific-yexamples ofhalogen-substituted hydro Y jcarbon radicals thatzRi'intheabove formula may; represent arezwchloro nethyl,chloroethyl, chloro- -phenylp dichl'orophenyL'. yethylt chlorophenyl, chlorocy'clohexylg phenyl chloroethyl', bromoethyl, lahromopropyl fluorophenyl, -iodopheny1, .brom'o- \itdlyktc ifiv'"4f J i I o butyl, butenyl amyl, isoamyl hexyl ioctyl, a ly etha lx e o l n w incl din bromophenyl, dibromophenyl, iodophenyl, fluorophenyl, chlorotolyl, bromotolyl chloroxylyl, chlo- Preferably R in Formula 1 is hydrogenQ l-Iowever, there" also" may be produced in accordance with the present invention compounds such, for instance, as those formula:

wherenfQR'; and R' have the same meanings as l 7 iven above with reference to Formula Ii The new compounds offlthi suinvention may be used, for example, as pha'r-maceuticals; plasticizers, fungicides, insecticides and as interme diates in the preparation of derivatives' thereof, e." g. .-hydrazino, carbazido;.1semicarbazido; ureido, amidine, methylol, methyleneyetci, derivativesiof the individualcompound embraced by Formula on 1. Our new compounds are especially (valuable in the preparation of synthetic resinouslco'mposi tions. Thus,they may be condensed with, .for

instance, aldehydes,---including. polymeric aldehydes, hydroxyaldehydes' andialdehydew'addition products; to yield condensation products having particular utility in the plastics and coating arts.

Such condensation iproducts are more iully'described and are specifically claimed-in bar" copending application Serial No; 458,725; filed-September 17, 942, asa continuation-in partfof the present application and assigned to the sarnj signee as the present invention. These newtriazine'. derivatives; also" maybe a compounded with rubber; fboth natural,..and isy'ntheticQ-to modify the properties of the rubber.

Various methods may be employed to-gproduce represented by the 'general mother liquor.

a variety o'f temperature andipressure conditions,

for example at normal, sub-normal'or at elevated temperatures and at atmospheric;; sub-atmospheric or super-atmospheric pressures. From the standpoint of convenience and' economy, normal or elevated temperature conditions'f'and atmosphericpressure usually-aremostdesirable A p The above reaction may be represented by the followlng: general equation;

nna

( hydrohalide acceptor) In the above equation}; represents a halogen atom; and n, R and R have the same meana ings as given above with reference toFormulafI.

In order that. those skilled in the art better may understand how the present invention may be carried into effect, the following examples are given by way of illustration and not by limitation. All parts are by weight.

Example '1 example illustr t the; b ba m me alpha'beta bisfidiamino s-t ia l' fil way of.

All of the above ingredientswith the exception 10f; the methyl alpha beta dichloropropionatev were mixed together, yieldingaclear solution. (The ester was then addecland the mass was a1- lowed to stand at roomtemperature for 5 days, 2 followed by heating. under reflux at theboiling temperature of the mass for 1 hour. Aftercoolmg, the precipitated product comprising methyl J alpha,beta-bis-(diamino s-triazinyl thio) pro- ?pionate was lfiltered oflf, washed well with water to remove soluble salts and dried. No-attempt .was made to obtain any. moreproduct from the A yield of 152 parts of the purified, dried compound was obtained. 1

' Example 2 Ethyl bis- (diamino s-triazinyl thio) acetate is prepared in essentially the same manner as described under Example lwith the exception that 1 78.5 parts of ethyl dichloroacetate are used in place of 78.5 parts of methyl alphabeta-dichlor H r lpropionate: v i

* Example 3 Propyl alphabeta-bisddiamino s-triazinyl thio) butyrate isprepared in essentially the same manner as-described under Example 1 with the r, ex ptiontha 144 rtslqi;propy1a p a eta=d1- methyl alpha,beta-dichloropropionate. 11 1 .5

brom'obiztyrate are .used' instead Jor- 78.5 parts. or

Methylywalphagbetabis-ldi- (methylaminoi s triazinyl thio 1i tpliopiqnate. is prepared in 6588;1- tiallythesame manner as described under ple. 1:'wit h Jthe exception that} 171* parts of niercapto di-(methylamino) s-triazine are used-in place of 143 partsofmercapto diamino s-triaz ine.

Example 5 Pee-1.3.1 bis-'(diamino s triazinyl thio) acetate is prepared in essentially the [same manner. as describecl' ujnder Example 1 with the exceptionthat "102 .51 .parts of phenyl dichloroacetate are used in 1aceforrzs,5p sor methyl,alpha beta-dichloroe propionate;

Illustrative examples of other compounds iembraced byFormulaI that may be produced in accordance with the presentinventionare sted below, including examples of aliphatic (e.g., alkyl,

alkenyl), aromatic and nuclearly halogenated aromaticesters.of'bis-(triazinyl thio) acetic and propionic acids:

;Methylbis (fliamino. setriazinylli thio) acetate, 1 which also may be named methyl bis- (2A- diamino s-triazinyl-6 thio) acetate, methyl 1 methyl bis- (4,6-diamino acetate. v r 5 a also 'lsob utyl bis-Qdiamino s triazinyl thio) acetate. Propenyl bis-(diamino s-triazinyl thio);.acetate I s-triazinyl 2 thio) .;Phenyl lbisidi-(methylamino) -s triaziny1 thio] acetate Tolyl bis-(diamino s-triazinyl thio) acetate Ethyl lpha,beta-bis-(di an ino s-triazinyl thio) Phenyl alphabeta-bis- (diamino s-triazinyl thio) fpropionatei v l 8 Methyl bis- [di (methylamino) s-triazinyl thiol acetate it 'i Zethylamino) s-triaziriyl im acetate M v *Phenyl bis-[di- '(isobutylamii1o) ljs triazinyl thio] ta e Fluorophenyl- .bis-[di-(cyclopentylamino) s-trlazinyl thio] acetate Tolyl bis- [di- (propenylamino) s-triazinyl thio'l acetate 7 Methyl alpha,beta-bis-(dianilino s-triazinyl thio) p r Pentyl beta-methyl alphabeta-bis- (diarnino: s-

l .triazinyl. thio) propionate Propyl alpha-,(chloropheriyl) .aminofs-htria ziriyl thio) propionate,

propionate -Ethy lalpha-ethyl alphabeta-bis (ditoluido. l striaziriyl thio) propionate Phe "yl T alphaaphenyl beta,beta-bis{( diamino xen l alpha-ethyl beta,beta -bis(diamino s mazinyl thiolpropionate f triazinyl thio) propionate Tolyl beta-propyl alpha,betabis-(diamino s-trlazinyl'thio) propionate Methyl alpha,beta-bis- (4-methylamino 6-amino s-triazinyl-z thio) propionate Ethyl .?alpha,alpha+bis-(4-anilino fi-amino s -triazinyl-2 thio) propionate. Chlorophenylbis-(diamino s-triazinyl thio) ace- Itatew F.:Chloronaphthyl bis-(diamino s-triazinyl thio) acetate W: Methyl bis- (ditoluido. s-triazinyl thio) acetate 1,Methyl bis-.[di-(iodoanilino) s-triazinyl thiol acetate rat:eaiiyiammoimnazmyl thio] propionate- I Cyclohexyl alpha,beta.-bis- [di- (cyclohexylamino) jitm] acetate Ben'zyl bia-(diamincis tri p'ropionate H V a l 1 c -M' hyl fbis M-Vnaphthylamino fir-iethylamino '.'.sl ""tri aziny1-".2 thioyacetate c v 1 i Plien'yl' a1pha,beta-'bis-'ldi maphthylarnino) striazinyl thio] propionate I v lodopherryl bis- (diamin-o-s-triazinylthio) acetate propionate Methallyl bis-( diamino s-triazinyl thio) acetate Tetradecyl bis-(diamino s-triazinyl thio) -a'eet'ate Octyl bis(diamino s-triazinyl thio) acetate V v Heirylalpha=,alpha-b is- (diamino s triazinylthio) *propio'nate p Heptyl -beta;beta bis (diamino *s-tria'ziny'l 'thio) propionate v In" a manner similar: to that described (above with particular reference to'the esters of his- ;(symmetrical -triazinyl vthio) rmonoca'rboxylic acids, corresponding derivatives of'ltheoasymtmetrieal .triazinestand of the vicinal tria'zinesmay be prepared' v I ,Whatwe claim as newva-ndidesireyto securegby Letters Patent of the United States is: 1

general formula ,1. Chemical compounds..corresponding-liiotlthe Where represents an integer an'd isat least 1 and not more than Z; R-representsamember of "the classcorisisting" offhydrogen and monovalent hydrocarbon and halo hydrocarborrradicals,- and "R" represents a member oftheclass consisting of monovalent aliphatic hydrocarbon radicals-and in'onovalent aromaticaridnutzlearl'y halogenated aromatic hydrocarbon radicals. J j ,t 2. Chemical compounds correspondingjt' {the general formula j i where n represents an integer and is at 1" and not more thanl2'gR'represents hydrogeniarid R represents a member of the class consisting of monovalent aliphatic hydroearbon radic 'als and monoyalent -aromaiticand; nuclearly halogenated aromatic hydrocarbon radicals.

-'(i(),, po.undsorresponding toi the general formula 1J3; :lGhemiealvcompoundscorresponding "t0 @the generathfiormula g" i 0 where n represents an integer and is at 1mm and not more than 2, R represents'hydrogen, and Rrepresents a monovalent aliphatic hydrocarboni radical.

4. Chemical compounds corresponding .to the where n represents an integer andis at'least"1 and not more than 2, R represents hydrogen, and

05 Rrepresentsamonovalent aromatic hydrocarhon-radical.v

'5. Chemical compounds .cOrrespOnding to the eneral'fformula a HR vNHR -|l N RHNC iwheren represents an. integer and is .at least 1 gandlnots-more'than 2,?Rrepresents a. member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals; and R represents a member of the class consisting of .Inoncvalenbaliphatic hydrocarbon radicals and monovalent aromatic and nuclearly halogenated --aromatic -hydrocarbon-radicals 6. An aliphatic ester of .bisdia-mino s-triazinyl thio) acetic acid. 7'7. An aalkyl ester of .bis-(diamino.s=triazinyl "thio) acetic acid. i g "'8. "An aliphatic ester of "'bis-(diamino s-tri- 'a z-inyl-thio) propionic acid. --An"--a1k -y1- ester* -of bis (dia-mino s-triazinyl 1 1'0. *AnearomatiC ester of bis- (diaminos-triazinyl thio)-aceticwacid. W I llfiPhen yl bisftdia-mino si-triazinylthio) ace- 13 iMethyl alphagbetaabis t'diamino s-triazinyl 1; thiol propionate. 1

514. ill'hevimethod of preparing :chemicaL comnot more than 2; R represents a memberzof the W0 class consisting of vhydrogen and monovalent hydrocarbon and halo hydrocarbon radicals, and "-R'--represents a meniber of theyclass consisting 6f monovalent a aliphatic hydroearbon radicals and monovaleht aromaticand nuclearly halozr5-=genated -ardmiti'c'iihydroeairbon radicals, s'aid pounds correspondingw to method comprising efi'ecting reaction, in the presence of a hydrohalide acceptor; between (1)" l a mercapto 'triazine 'eral formula corresponding to the genfI HR g of monovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals, said where R has the meaning above given, and (2) I e {an ester of a dihalogenatedmonocarboxylic ali-, phatic acid corresponding to the general formula where X represents a halogenatom, and n, Rand R have the same meanings as given above, the

said reactants being empl'oyedyin the ratioof at least two mols of themercapto trlazine of (1) per mol of the ester'oi 2). i l 15. Themethod of preparing chemical comthe general formula i ITTHR where nQrepresents an integer and is at least 1 and; not more than 2, R represents amember of the class consisting ofhydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and

' Rf represents a memberof the class consisting alpha,beta-bis-(diamino, s triazinylthio) pro- 1 metlnod comprising effecting reaction, in the presence of an alkali-metal hydroxide, between -(l) a merca-pto triazine corresponding to the general formula NHR 1 tg 1 i BEN-(III). (|3SH a n N i where R has the meaning above given, and (2) an ester of a dihalogenated monocarboxylic aliphatic acid corresponding to the generalformula where X represents a chlorine atom,- and and' R have the same meanings as given above, the i said reactants being employed in the ratio of at least two mols of the mercapto triazineof (1) per mol of the ester of (2). n

16. The method of preparing methyl pionate which comprises efiecting reaction, in

the presence of an alkali-metal hydroxide, be-

tween methyl alpha,beta-dichloropropionate and mercapto diamino s-triazine in the ratio of. one

mol of the formertoat least'twofmolsof the latter.

- GAETANOF. DALELIO.

JAMES W. UNDERWOOD;

Certificate of Correction Patent No. 2,328,959. September 7, 1943. GAETANO F. DALELIO, ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 21, for mole read mol; and second column, line 24, for alpha-betaread alpha,beta-; line 26, for alpha-alpharead -aZpha,aZpha-; and second column, line 36, for alphabetaread alpha,beta-; page 3, first column, line 10-15, for

(hydrohtalide accep or +XzC "Rh-C O 0 R read 2(hydrohalide acceptor +XzOnRh-1COOR' page 4, first column, line 31, for bis(diamino read bis-(diamino; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 2nd day of November, A. D. 1943.

[SEAL] HENRY VAN ARSDALE,

Acting Commissioner of Patents. 

